Litvinenko, 43, an outspoken critic of Putin who fled Russia, died after drinking green tea laced with the rare radioactive isotope at London's Millennium Hotel.
An inquiry led by British judge Robert Owen found that former KGB bodyguard Andrei Lugovoy and another Russian, Dmitry Kovtun, poisoned Litvinenko as part of an operation directed by Russia's Federal Security Service (FSB), the main heir to the Soviet-era KGB.
"The FSB operation to kill Mr Litvinenko was probably approved by Mr Patrushev, then head of the FSB, and also by President Putin," Owen said.
"I have concluded that there is a strong probability that when Mr Lugovoy poisoned Mr Litvinenko, he did so under the direction of the FSB. I have further concluded that Mr Kovtun was also acting under FSB direction," he said.
The judge said he was sure Lugovoy and Kovtun had placed the polonium 210 in the teapot at the Millennium Hotel's Pine Bar on November 1, 2006.
Traces of the highly radioactive substance were found at several sites across the city.
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